Processes and methods using chlorine dioxide to remove NOx and SOx from marine exhaust

ABSTRACT

Integrated exhaust gas systems, methods, and processes are disclosed that includes pretreatment, treatment and post-treatment processes arranged in a variety of reaction environments to address varied application requirements and end product requirements is described in this disclosure. In addition, a contemplated ballast water treatment system—that can be used in combination with the integrated exhaust gas systems can treat seawater and return it to storage within the vessel or send treated water back to the sea. This system can be sized to treat the seawater as it is leaving the ship without prior treatment, while the seawater is aboard or treat the seawater that is within the ship and add any additional treatment to the water, as the seawater leaves the ship. This system is not involved with pumping the seawater into the ship or filtering the water prior to storage as ballast water.

This patent application is a continuation-in-part of U.S. patent application Ser. No. 15/087,713, which was filed on Mar. 31, 2016, which is a continuation-in-part of U.S. patent application Ser. No. 14/666,199, which was filed on Mar. 23, 2015, which is a continuation of U.S. patent application Ser. No. 14/537,834, which was filed on Nov. 10, 2014 and which is now U.S. Pat. No. 9,272,257, which is a continuation of U.S. patent application Ser. No. 14/126,403, which was filed on Dec. 13, 2013, now U.S. Pat. No. 8,883,105, which is a National Phase application of PCT Application No.: PCT/US2013/020586, which claims priority to U.S. Provisional Application No. 61/584,347 filed on Jan. 9, 2012, U.S. Provisional Application No. 61/656,192 filed on Jun. 6, 2012, U.S. Provisional Application No. 61/715,146, and U.S. Provisional Application No. 61/715,149 filed on Oct. 17, 2012, all of which are incorporated by reference in their entirety.

FIELD OF THE SUBJECT MATTER

The field of the subject matter is removal of NOx and SOx impurities and compounds from marine vessel exhaust and control of invasive species in ballast water.

BACKGROUND

Environmental pollution is a problem adversely affecting the planet and its inhabitants. Fortunately, a majority of the individuals recognize the necessity of reducing the emission of greenhouse gases and the necessity of protecting our oceans.

One large source of pollution is maritime vessels, by virtue of the fact that the oceans cover a majority of the planet and there is a lot of maritime vehicle traffic. There are a number of conventional technologies that are designed to try to control the air pollution caused by combustion and water pollution associated with ballast water that is associated with maritime vessels, but it remains to be seen whether any of those technologies can successfully mitigate that pollution.

The International Maritime Organization (IMO) provides guidance and regulation for maritime vessels worldwide. There are three main areas identified by IMO as being the most destructive to our environment: exhaust sulfur dioxide (SO₂), exhaust oxides of nitrogen (NOx), and ballast water pollution associated with aquatic organisms.

Various literature discusses that seawater may be useful method for removing most of the SO₂ generated in combustion devices aboard vessels. Unfortunately, there are few published scientific studies addressing the removal efficiencies of seawater SO₂ scrubbers.

One study from Italy by G. Caiazzo (G. Caiazzo—Seawater SO₂ scrubbing in a tower for marine applications—Universita degli Studi di Napoli Federico II, Via Claudio 21, Napoli 80125, Italy) evaluates SO₂ removal efficiency base research that compares seawater scrubber residence time, liquid flow rate and SO₂ concentration. His findings show a maximum removal efficiency of 93% with a 3.4 second reaction residence time and a liquid to gas ratio of 0.01 to 1. This is a long residence time that will require a large scrubber vessel and an enormous amount of seawater flow through a full-scale device. It is noteworthy that the reported removal efficiency will not meet 2016 and 2020 International Maritime Organization (IMO) rules for SO₂ emissions when the vessel is using conventional fuels with 3.5% sulfur content. Those operating marine vessels will have to make a decision between using more expensive fuels and paying for combustion device upgrades to accommodate the low sulfur fuels or adding an additional SO₂ abatement device.

Most of the papers and patents that describe seawater treatments for SO₂ or SO_(x) describe coarse spray devices or countercurrent scrubbers. CA1303822 discloses improved SO₂ adsorption by recirculating aqueous stream of sea water containing magnesium hydroxide and magnesium sulfite in a countercurrent packed bed scrubber.

Statoil's refinery at Mongstad, Norway has been using a seawater flue gas desulfurization unit that has a countercurrent packed bed scrubber. (See http://www.ogj.com/articles/print/volume-89/issue-26/in-this-issue/refining/seawater-scrubbing-removes-so2-from-refinery-flue-gases.html)

WO 1992008541 claims SO₂ and NOx abatement in a two-stage process that involves spray of seawater into ducting that precedes the first stage. The first stage apparently bubbles the exhaust gas into a pool of seawater for SO₂ abatement. The second stage NOx treatment is done in a packed bed scrubber that adds urea (NH₂)₂CO to seawater at ambient temperatures. The patent application does not clearly identify the packing material in the NOx scrubber and there is no mention of a catalyst.

EP 3132839 describes a two-stage packed bed scrubber using seawater that has been pH adjusted by the addition of an alkaline material. There is no disclosure of removal efficiency.

There are several patents and patent publications directed to marine NOx abatement using SCR technology. None were found for marine NOx abatement using (ClO₂)^(o). Some patents for selective catalytic reduction or “SCR” technology report removal efficiencies between 85% and 93%. These also incorporate soot blowers to clean off the catalyst beds. CN101922333B candidly identified the challenges associated with SCR catalyst poisoning and clogging associated with processing exhaust generated from high sulfur marine fuels. The concerns include: a) SCR catalyst can be poisoned by sulfur fuels; b) marine engine operating conditions change frequently—at low load conditions the exhaust temperature is too low to effectively utilize the SCR technology; and c) for safety reasons ships are unable to use ammonia and are required to use 40% aqueous urea which has supply and cost considerations. The patent clearly specified the reported technology is only applicable to marine fuels with less than 1.5% sulfur.

To this end, it would be desirable to provide methods and related apparatus that can address exhaust sulfur dioxide (SO₂), exhaust oxides of nitrogen (NOx), and ballast water pollution associated with aquatic organisms that includes: a) a process that can be stand-alone or can be included with other abatement technologies, b) serves the marine industry and other industries that utilize or have access to seawater, c) has relatively high removal efficiencies of NOx and SOx impurities and compounds, as compared with conventional technologies, and d) has a relatively low overall operating cost, as compared with conventional technologies.

SUMMARY OF THE SUBJECT MATTER

Specifically, a pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a water supply line that supplies a liquid; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of liquid across the interior surface of the reaction chamber; a pH sensor coupled to the water supply line; at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas by converting it to sulfate ions.

A pretreatment method or process for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: providing a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; providing a water supply line that supplies a liquid; providing an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; providing a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of liquid across the interior surface of the reaction chamber; providing a pH sensor coupled to the water supply line; providing at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and providing a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecule from the exhaust gas by converting it to sulfate ions.

In another embodiment, a pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a seawater supply line that supplies seawater; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the seawater supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of seawater across the interior surface of the reaction chamber; a pH sensor coupled to the seawater supply line; at least one chemical metering pump coupled to the pH sensor and the seawater supply line, wherein the pump can provide an alkaline material into the seawater supply line to adjust the pH of the seawater before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas by converting it to sulfate ions. This conversion reaction proceeds as follows: 5SO₂+2ClO₂+6H₂O→5H₂SO₄+2HCl  [1]

A pretreatment method or process for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: providing a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; providing a seawater supply line that supplies seawater; providing an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; providing a gas atomization nozzle array that is coupled to the seawater supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of seawater across the interior surface of the reaction chamber; providing a pH sensor coupled to the seawater supply line; providing at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and providing a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecule from the exhaust gas by converting it to sulfate ions.

A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas is described that comprises: a contemplated pretreatment system, wherein the second end of the reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; and an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the first reaction chamber travels from the outlet end of the first reaction chamber to the first end or inlet end of the second reaction chamber.

Another NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, is described that comprises: a contemplated pretreatment system, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; and an inlet for introducing chlorine dioxide into the reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with non-ionic chlorine dioxide.

A method of NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, includes: providing a contemplated pretreatment system, wherein the second end of the reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; providing an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the first reaction chamber travels from the outlet end of the first reaction chamber to the first end or inlet end of the second reaction chamber; and treating the exhaust gas or gas to be treated with chlorine dioxide.

A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas is also disclosed that comprises: a contemplated pretreatment system, wherein the second end of the reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the pretreatment reaction chamber travels from the outlet end of the pretreatment reaction chamber to the first end or inlet end of the second reaction chamber; and an inlet for a post-treatment chamber that is coupled with the second end of the second reaction chamber, wherein at least one product of the second reaction chamber travels into the inlet of the post-treatment chamber.

A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas is disclosed that comprises: a contemplated pretreatment system, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; an inlet for introducing chlorine dioxide into the pretreatment reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with non-ionic chlorine dioxide; and an inlet for the introduction of seawater, potable water with additional metal hydroxides, tainted water with additional metal hydroxides, or pure water with additional metal hydroxides in order to neutralize the mineral acids that are produced reaction chamber.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows an example of and integrated package of a contemplated exhaust gas treatment and ballast water treatment.

FIG. 2 shows an example of a contemplated process consisting of three modules: exhaust gas SOx pre-treatment in one module, exhaust gas NOx/SOx treatment and post gas treatment in a separate module and ballast water treatment in a third module.

FIG. 3 shows in detail the actual (ClO₂)^(o) dosing and control methodology for the ballast water module included in the rectangle marked “E” on FIG. 2.

FIG. 4 shows an example of a contemplated process consisting of two modules: exhaust gas SOx pre-treatment, NOx/SOx scrubbing and post scrubbing gas treatment are combined in one module, and ballast water treatment in a separate module. Both modules share the same chemical generation system.

FIG. 5 shows an example of the contemplated process consisting of three modules: exhaust gas SOx pre-treatment is in one module, NOx/SOx scrubbing and post scrubbing gas treatment are combined in a second module, and ballast water treatment in a third module. All modules share the same chemical generation system.

FIG. 6 shows a contemplated instrumentation and control network for the integrated group of modules included in this process.

FIG. 7 shows an exhaust gas treatment portion of the contemplated process in an expanded view. The exhaust SOx pretreatment is in one module and a second module combines NOx/SOx scrubbing and post scrubbing gas treatment.

FIG. 8 shows the exhaust gas treatment portion of the contemplated process in an expanded view. The exhaust SOx pretreatment, NOx/SOx scrubbing and post scrubbing gas treatment are combined in a single module.

DETAILED DESCRIPTION

To address the problems with the prior art and conventional technologies, methods, systems, processes, and related apparatus that can address exhaust sulfur oxides (SOx), including sulfur dioxide (SO₂), exhaust oxides of nitrogen (NOx), and ballast water pollution associated with aquatic organisms have been developed and are disclosed herein that include: a) a process that can be stand-alone or can be included with other abatement technologies, b) serves the marine industry and other industries that utilize or have access to seawater, brackish water, or potable water; c) has relatively high removal efficiencies of NOx and SOx impurities and compounds from exhaust gas, as compared with conventional technologies, d) has a relatively low overall operating cost, as compared with conventional technologies, and e) has relatively good ballast water biological abatement results, as compared with conventional technologies. Contemplated embodiments that utilize seawater overcome several challenges, including the challenge that conventional processes are detrimentally impacted by changes in seawater alkalinity.

A system of treatment processes for marine exhaust and ballast water treatment is disclosed herein, wherein each phase individually contains unique characteristics, but when combined in various combinations surprisingly and synergistically work together to produce additional unique characteristics to meet specific abatement requirements.

There are four distinct processes and systems, with corresponding apparatus, that will be described in detail herein—each alone and in combination with each other:

-   -   Pretreatment of sulfur dioxide (SOx) in marine combustion         exhaust (marine exhaust)     -   Treatment of nitrogen oxides (NOx) and SOx in marine exhaust     -   Post-treatment of reaction products from earlier stages to         produce compounds that are environmentally friendly and/or may         have commercial value     -   Marine ballast water treatment of invasive and regulated marine         organisms

The contemplated disclosures may be combined among themselves and/or with other known/conventional exhaust gas technology to provide abatement advantages that have not been previously reported in the literature.

Contemplated embodiments include a series of methods, systems, and processes that utilize gas phase chlorine dioxide and other compounds and components to remove nitrogen oxides and sulfur oxides from combustion exhaust and abate biological organisms in marine ballast water. As will be described herein and disclosed in the examples, contemplated systems and processes for treating exhaust gas and ballast water can be accomplished in a module or a combination of modules that can share a common source of chlorine dioxide input or generation.

An integrated solution that addresses the SOx, NOx, and ballast water pollution issues using the same molecule—chlorine dioxide—in three different reactions/applications is disclosed herein. A contemplated SOx pre-treatment scrubber module overcomes limitations found in other patented and published SO₂ or SOx scrubbers. Cost and space savings are also realized by integrating and utilizing contemplated embodiments because the NOx/SOx removal/abatement, along with the ballast seawater treatment, can utilize the same chemical constituents and can take place in the same process reactor/process reactor system.

There are a number of advantages and features of contemplated processes that include ballast seawater treatment, which include:

-   -   A contemplated ballast water treatment system can treat seawater         and return it to storage within the vessel or send treated water         back to the sea. This system can be sized to treat the seawater         as it is leaving the ship without prior treatment, while the         seawater is aboard or treat the seawater that is within the ship         and add any additional treatment to the water, as the seawater         leaves the ship. This system is not involved with pumping the         seawater into the ship or filtering the water prior to storage         as ballast water.     -   The automated control and sensor system for the ballast water         treatment system is part of the overall contemplated control         system. This provides the vessels crew with the ability to         determine the concentration of (ClO₂)^(o) desired in the ballast         water and verify that the desired concentration is present.     -   The ballast water treatment system depicted in FIG. 3 utilizes         the same (ClO₂)^(o) generator that supplies gas phase (ClO₂)^(o)         to the contemplated NOx and SOx abatement technology, which         saves space on the ship or vessel. The generator can be sized to         do both tasks at the same time or to just handle one at a time.     -   A contemplated system utilizes an infrared detector that         determines (ClO₂)^(o) concentration via unique optical         absorption characteristics. This choice of technology avoids the         measurement confusion and problems associated with the use of         oxidation-reduction potential or “ORP” for determination of         (ClO₂)^(o) concentration. ORP by its very design measures the         oxidation and reduction of any compounds in the liquid being         tested, which leads to confusion in complicated solutions like         seawater with many ions that can influence an ORP reading.     -   A contemplated system automatically measures and adjusts the         seawater pH to a predetermined set point that is compliant with         IMO regulations and other regulations. The pH adjustment system         can be sized to treat the seawater as it is being returned to         the ocean without prior adjustment while onboard the vessel or a         smaller version of the technology can pretreat the seawater pH         while being held on the vessel and make minor adjustments as the         seawater is discharged to the sea.

The characteristics and uniqueness resulting from combinations of processes is best described by defining the physical structures that are utilized as a part of this disclosure. As used herein, the term “chamber” means a contained reaction environment with an access point near one end for the introduction of exhaust gas, a volume of any shape for the containment of chemical and physical transformations to the exhaust gas, a discharge point for the treated exhaust gas that is at or near the opposite end of the chamber, various connection points for the introduction of other chemicals in gas or liquid phase, drains for liquid waste products and physical devices within the volume for mixing and other physical change to the reaction mixture. A chamber can contain a single process or contain two or more processes that occur in sequence as the exhaust gas moves from one end of the chamber to the other.

As used herein, the term “module” means a physically distinct vessel that is connected in series or in parallel with other modules to create the combined treatment process. Each module is unique in its combination of chambers. Some have just one chamber that facilitates a single process, some have a single chamber that provide a series of processes, and some include a series of chambers each facilitating one or more processes. The Examples section conveys some of the possible combinations of features, but it should be understood that these examples are not limiting and one of ordinary skill in the art should understand how these modules and chambers can be utilized alone or in combination. Each contemplated process will be described separately, in order to establish a baseline understanding of each one, and then the combination of those processes and their advantages will be disclosed for reference purposes.

Specifically, a pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a water supply line that supplies a liquid; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of liquid across the interior surface of the reaction chamber; a pH sensor coupled to the water supply line; at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas by converting it to sulfate ions.

A pretreatment method or process for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: providing a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; providing a water supply line that supplies a liquid; providing an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; providing a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of liquid across the interior surface of the reaction chamber; providing a pH sensor coupled to the water supply line; providing at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and providing a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecule from the exhaust gas by converting it to sulfate ions.

In another embodiment, a pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a seawater supply line that supplies seawater; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the seawater supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of seawater across the interior surface of the reaction chamber; a pH sensor coupled to the seawater supply line; at least one chemical metering pump coupled to the pH sensor and the seawater supply line, wherein the pump can provide an alkaline material into the seawater supply line to adjust the pH of the seawater before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas by converting it to sulfate ions. This conversion reaction proceeds as follows: 5SO₂+2ClO₂+6H₂O→5H₂SO₄+2HCl  [1]

A pretreatment method or process for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: providing a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; providing a seawater supply line that supplies seawater; providing an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; providing a gas atomization nozzle array that is coupled to the seawater supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets that create a high surface area of seawater across the interior surface of the reaction chamber; providing a pH sensor coupled to the seawater supply line; providing at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and providing a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecule from the exhaust gas by converting it to sulfate ions.

As contemplated herein, the “water supply line” may provide any type of water, including seawater, pure water, potable water, or tainted water. In some embodiments, metal hydroxides, carbonates, biocarbonates, ammonia, or a combination thereof—herein referred to as “alkali materials” may be added to the water. As contemplated herein, the “seawater supply line” provides seawater alone or with additional materials, as described herein.

As used herein, the phrase “small diameter liquid droplets” refers to droplets that are less than or equal to about 30 microns in mean diameter. In some embodiments, small droplets refer to droplets that are less than or equal to about 25 microns in mean diameter. In other embodiments, small droplets refer to droplets that are less than or equal to about 20 microns in mean diameter. In yet other embodiments, small droplets refer to droplets that are less than or equal to about 10 microns in mean diameter. It should be understood that these contemplated small diameter liquid droplets also have a higher surface area when combined with other small diameter liquid droplets, as compared with a combination of larger diameter liquid droplets.

In some embodiments, the droplets may be formed by gas atomizing nozzles or non-gas atomizing nozzles, depending on the application needed at the time. In other embodiments, atomizing nozzles may comprise one of the two different process forms: externally mixed gas/liquid atomizing nozzles or internally mixed gas/liquid nozzles. The BETE XAPF is an example of a gas atomizing flat fan internal gas liquid mixing nozzle. The BETE XAER is an example of a gas atomizing round spray external mix nozzle. In yet other embodiments, contemplated atomizing nozzles may be of a gas-type or a hydraulic-type atomizing nozzle.

A NOx, SOx, or a combination thereof abatement or scrubbing process, system, or method for marine vessel flue gas, herein referred to as the NOx/SOx process, is disclosed, which may occur by itself in a chamber or be combined with the previously described pretreatment SOx process in a single chamber. When the chamber used for the NOx/SOx process does not include the SOx pretreatment process, the second end of the pretreatment system reaction chamber is coupled with a first end of the chamber containing the NOx/SOx process.

In NOx/SOx process applications that include the SOx pretreatment process and the NOx/SOx process in the same reaction chamber the gas inlet at or near the first end of the combined process chamber is connected to the exhaust gas stream. In both embodiments, the chamber or portion of the chamber used for the NOx/SOx process, there is an inlet for introducing chlorine dioxide into the portion of the reaction chamber used for the NOx/SOx reaction. In addition, the NOx/SOx portion of a reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated is drawn through the length of the reaction chamber by lower differential pressure at the discharge or second end of the chamber used for NOx/SOx than the inlet or first end of that same reaction chamber.

The reactions occur in accordance with the following equations in all types of water: 5NO+2(ClO₂)^(o)+H₂O→5NO₂+2HCl  [2] 5NO₂+(ClO₂)^(o)+3H₂O→5HNO₃+HCl  [3] 5SO₂+2(ClO₂)^(o)+6H₂O→5H₂SO₄+2HCl  [4]

When seawater is used in the process, equation 5 is also applicable: 6SO₃ ⁻²+2(ClO₂)^(o)12H⁺→H₂S₂O₆+4H₂SO₄+2HCl  [5]

The SOx pretreatment process, NOx/SOx process and post treatment processes are combined in a number of embodiments with other pretreatment NOx abatement processes such as Selective Catalytic Reduction (SCR) described in prior art. Each of embodiments is identified as a unique module. Some of the modules are described in the Examples section.

There are several contemplated post-treatment processes, methods, and systems that are disclosed herein and that are activated or undertaken in the post-treatment reaction chamber or post-treatment module. Each of these is a unique process and all of them described herein are grouped as uniquely identified members of the post-treatment processes collection, which includes, but is not limited to, an acid neutralization post-treatment process, a sodium nitrate/nitrate production post-treatment process, an ammonium sulfate production post-treatment process, and/or an ammonium nitrate and ammonium chloride production post-treatment process.

A contemplated acid neutralization post-treatment process neutralizes acids made in the SOx pretreatment and NOx/SOx treatment processes by combining them with seawater, pure water, potable water, or brackish waters, sometimes in combination with additional metal hydroxides, to neutralize the mineral acids by converting them into salts. The use of seawater has advantages over other waters in this application because of the inherent pH buffering associated with this particular liquid. In some cases, the use of seawater alone is sufficient to neutralize the mineral acids generated in the SOx pretreatment and NOx/SOx treatment processes. The neutralization reactions may occur according to the following equations: HCl+NaOH→NaCl+H₂O  [6] HNO₃+NaOH→NaNO₃+H₂O  [7] H₂SO₄+NaOH→Na₂SO₄+2H₂O  [8]

It should be understood that this post-treatment process can occur in a reaction chamber affixed or coupled to the effluent, second, or outlet end of the NOx/SOx treatment chamber, wherein the exhaust gas or gas to be treated leaving the second end of the chamber used for NOx/SOx abatement immediately enters the first opening at or near the beginning of the chamber used for post-treatment.

The post-treatment process chamber can also be a completely independent vessel. In this embodiment, there is a connection of the second opening of the NOx/SOx process chamber with an opening at or near the first end of the post-treatment module. In either case, the exhaust gas or gas to be treated is pulled through the post treatment chamber or series of chambers by a lower pressure at the discharge end of the post-treatment chamber(s) than at the inlet end of the post treatment chamber(s). This process of using differential pressures also aids in moving exhaust gas or gas to be treated through the pre-treatment phase, through the treatment phase, and also through the post-treatment phase, as disclosed herein.

The post-treatment chamber also includes one or more tubes or lines for the introduction of water having a pH adjustment by the addition of alkaline material. This water is used for production of a blanket of low diameter droplets that covers, in some embodiments, a majority of the surface, and in some instances, the full interior surface, of the reaction chamber by a nozzle or nozzles. It should be understood that there may be cases where a small portion of the interior is not “blanketed” by droplets, because of the type of nozzle used or the interior shape of the chamber. In those instances, the process will still function very well. This also applies to the pre-treatment and treatment stages. The chamber may also include one or more turbulence inducing devices, wherein the turbulence inducing device is a stationary device.

In another embodiment, a sodium nitrite/nitrate production post-treatment process occurs in a module or modules of the same design described for the acid neutralization post-treatment process. But they differ from one another in the chemistry or chemicals added to the chamber through the nozzle(s). This post-treatment process requires the NOx/SOx process to convert not less than half of the NO in the NOx exhaust gas stream into NO₂. The treated exhaust gas is introduced into the first end of post-treatment chamber, wherein sodium hydroxide or other metal hydroxides—plus a process promoter of specific type described in Table 1 in quantities of between 5 and 10% of the volume of metal hydroxide—are added.

The equation for this process is shown in equation 9. The molecules associated with the placeholder (**) are shown in Table 1: 2NaOH+NO₂+NO+(**)→2NaNO₂+H₂O  [9]

TABLE 1 ** REACTION PERCENT REMOVAL PROMOTING COMPOUNDS EFFICIENCY H₂O₂ 85-90% O3 95% NaClO 90-95% Ca(ClO)₂ 95-100%

In yet another embodiment, ammonium sulfate production post-treatment process occurs in a module or modules of the same design described for the acid neutralization post-treatment process. But, they differ from one another in the chemistry or chemicals added to the chamber through the nozzle(s). This post-treatment requires the NOx/SOx process to convert not less than half of the NO in the NOx exhaust gas stream into NO₂. The treated exhaust gas is introduced into the first end of post-treatment chamber, wherein ammonium sulfite is added through nozzles to react with the exhaust gas mixture, thereafter producing ammonium sulfate. 2NO₂+3(NH₄)₂SO₃→3(NH₄)₂SO₄+N₂+½O₂  [10] NO+NO₂+3(NH₄)₂SO₃→3(NH₄)₂SO₄+N₂  [11]

In yet another embodiment, ammonium nitrate and ammonium chloride production post-treatment process occurs in a module or modules of the same design described for the acid neutralization post-treatment process. But, they differ from one another in the chemistry or chemicals added to the chamber through the nozzle(s). This post-treatment requires the NOx/SOx process to convert not less than about 98% of the NO in the NOx exhaust gas stream into NO₂ in accordance with equation 2 and note less than about 98% of the NO₂ in the gas stream to HNO₃ and HCl in accordance with equation 3. The treated exhaust gas is introduced into the first end of post-treatment chamber, wherein ammonia is added through nozzles to react with the exhaust gas mixture, thereafter producing ammonium nitrate and ammonium chloride. NH₃+HCl→NH₄Cl  [12] NH₃+HNO₃→Nh₄NO₃  [13]

The ballast water treatment process is independent of the exhaust gas treatment in most embodiments, other than the fact that the NOx/SOx treatment and the ballast water treatment systems both utilize gas phase chlorine dioxide that can be generated in one location.

In some embodiments, contemplated apparatus and methods can treat ballast water and return it to storage within the vessel or send the treated water back to the sea. A contemplated system can be sized to treat the seawater as it is leaving the ship without prior treatment, while the seawater is aboard or treat the seawater that is within the ship. Additional treatment can be added to the seawater as it leaves the ship.

Recognition of the novelty of the solutions described herein where the applications utilize the same chemical—chlorine dioxide—is facilitated by an understanding of this molecules chemical characteristic. It is also important to note that the term “chlorine dioxide” has been misapplied in patent and non-patent literature. The name is assigned to one of three ionic variations of the ClO₂ molecule.

Chlorine dioxide is capable of existing in three ionic states. Table 1 provides the IUPAC names for them and describes their ionic characteristics. Again, this distinction is made because the ionic form of this ClO₂ molecule has mistakenly been called “chlorine dioxide” and that ionic form of ClO₂ will not achieve the results described herein because that molecule has dramatically different chemical characteristics than the non-ionic form of ClO₂ or as referred to herein, (ClO₂)⁰.

TABLE 2 Formula used in Conventional the present Preferred IUPAC Name Ionic charge Formula disclosure Chlorine dioxide 0 ClO₂ (ClO₂)⁰ Chlorite −1 ClO₂ ⁻ (ClO₂)⁻ Chloryl +1 ClO₂ ⁺ (ClO₂)⁺

Non-ionic chlorine dioxide is the common denominator shared by the integrated NOx, SO₂ and SON, and ballast water treatments for marine vessels described herein.

The success in gas phase abatement of NO_(x), SO_(x) and ballast water decontamination is only possible when the non-ionic version of the ClO₂ molecule is utilized. The technology disclosed herein is exclusively related to the non-ionic form of the (ClO₂)⁰ molecule; however, other forms may be present during treatment—either because of the availability of chemical states or because they are being utilized for other purposes.

Contemplated embodiments can eradicate most planktonic and bacterial organisms from seawater used as ballast in vessels. This technology utilizes (ClO₂ ^(o)) suspended in water that is made on an as needed basis aboard the vessel. The) (ClO₂ ^(o)) is a selective biocide that is applied more often in industry and municipal water treatment applications, because of the fact that is has less damaging effects to the environment and human health than chlorine. It does not form hydrochlorous acids in water; it is also a more reactive biocide at seawater pH ranges. Automated control and sensor systems for the ballast water treatment system are a part of the contemplated systems. These control and sensor systems provide the crew with the ability to determine the concentration of chlorine dioxide desired in the ballast water and verify that the desired concentration is present.

It is contemplated that in some embodiments, the ballast water treatment system uses the same chlorine dioxide generator system as the NOx and SOx abatement systems, which means that this entire system can be compact and efficient.

A ballast water treatment system for producing treated seawater is described herein that includes: a reaction chamber, wherein the reaction chamber is located within a vessel; an inlet for introducing chlorine dioxide into the reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device; a second inlet for the introduction of seawater, into the reaction chamber; and an outlet from the reaction chamber, wherein the treated seawater is returned to a storage facility within the vessel or is returned to the sea. As with the other systems disclosed herein, at least one additional treatment component can be provided into the system, such as at least one alkaline material, at least one pH adjustment component, or other components, as needed.

Also, as with other systems disclosed herein, contemplated ballast seawater systems may comprise an automated control and sensor system. These control and sensor systems are designed to monitor and control the concentration of chlorine dioxide, at least one additional treatment component, or a combination thereof. In some embodiments, a contemplated control and sensor system is operatively coupled with an infrared detector. In these embodiments, a contemplated infrared detector is utilized to measure the chlorine dioxide concentration in the reaction chamber.

In some embodiments, the automated control and sensor system measures the pH of the seawater. In some embodiments, this same system can measure and adjust the pH of the seawater. The pH of the seawater may be measured and adjusted when the seawater is in the reaction chamber. In other embodiments, the pH of the seawater may be measured and adjusted after the seawater exits the reaction chamber.

A method of treating ballast seawater for producing treated seawater is also described that includes: providing a reaction chamber, wherein the reaction chamber is located within a vessel; providing an inlet for introducing chlorine dioxide into the reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device; providing a second inlet for the introduction of seawater, into the reaction chamber; providing an outlet from the reaction chamber; and treating the seawater with chlorine dioxide, wherein the treated seawater is returned to a storage facility within the vessel or is returned to the sea.

In summary, contemplated embodiments provide several advantages in marine applications over other available and conventional technologies for NOx, SOx exhaust gas treatment and ballast water treatment, including: a) saving space and cost, because contemplated embodiments utilize the same chemical generation equipment for the core aspects of all three processes; b) contemplated embodiments provide 100% backup for NOx and SOx abatement when integrated with SCR or other NOx abatement technology, wherein contemplated embodiments provide this backup with only a fraction of the space or cost required for any other 100% backup technologies; c) contemplated embodiments are very adaptable, in that they can operate as a stand-alone system or as an integrated package with other abatement technologies, embodiments can be separated into autonomous separate modules when just one or more of the contemplated systems are required for a specific project requirement; and d) contemplated embodiments will continually meet future emission compliance requirements without an equipment upgrade.

As an example, contemplated integrated NOx/SOx reactor and generator modules can be provided alone to solve compliance challenges for a vessel with under-performing abatement equipment, when the vessel is required to meet more stringent international IMO or national emission requirements for NOx and SO₂.

In other embodiments, contemplated abatement systems are capable of meeting changing NOx and SO_(x) removal efficiency requirements by merely revising a removal efficiency set-point. The initially supplied reaction vessel and generator are adaptable and cost effective, because they only generate (ClO₂ ^(o)) on an as needed basis. This “as needed” feature eliminates ongoing wasted chemical costs and the extra upfront equipment cost associated with the purchase of extra capacity in a conventional scrubber.

The following Examples illustrate how the embodiments disclosed herein can be utilized; however, it should be understood that these Examples are not limiting and are used to show some of the specific embodiments that are a part of the broad scope of the technology disclosed herein.

EXAMPLES Example 1

A NOx, SOx, or a combination thereof abatement or scrubbing process (NOx/SOx process) for marine vessel flue gas, can be accomplished in a single-chambered module as described generally earlier. A contemplated process is included in this example.

Exhaust gas is drawn into the first end of the NOx/SOx reaction chamber and continues to move through the chamber to the second end of the chamber. The (ClO₂)^(o) as gas, mist, or droplets is drawn or pushed into a contemplated NOx/SOx reaction chamber at a point downstream of the first end of the chamber. The exhaust gas and (ClO₂)^(o) are drawn into and through the reaction chamber by the lower exhaust gas pressure at the second end of the chamber, as compared to the first end of the chamber.

In embodiments that introduce (ClO₂)^(o) as a gas, there is no need to push the gas into the reaction chamber. It is safer to allow it to be pulled into the chamber by the differential pressure between the inside of the reaction chamber and the ambient pressure in which the gas is stripped from liquid during preparation for this application. In embodiments that introduce (ClO₂)^(o) that has been suspended in a liquid into the reaction chamber, a low pressure pump can provided to facilitate moving the liquid into the chamber.

Downstream of the point (ClO₂)^(o) is introduced into the reaction chamber, the (ClO₂)^(o) and exhaust gas are pulled through a static mixer or mixers of any conventional design. When gas phase (ClO₂)^(o) is introduced into the reaction chamber, the static mixers can be placed immediately downstream of the point where the (ClO₂)^(o) is added. In some embodiments when (ClO₂)^(o) is introduced into the reaction chamber as a mist or droplets, the static mixers are place sufficiently downstream of the point where the (ClO₂)^(o) is introduced to allow the mist or droplets to evaporate. The mixed gases continue down the length of the reaction chamber while the NOx and SO₂ abatement reactions described in equations [2], [3] and [4] occur. 5NO+2(ClO₂)^(o)+H₂O→5NO₂+2HCl  [2] 5NO₂+(ClO₂)^(o)+3H₂O→5HNO₃+HCl  [3] 5SO₂+2(ClO₂)^(o)+6H₂O→5H₂SO₄+2HCl  [4]

In some embodiments, NOx/SOx abatement process occurs in a module with two chambers. In this two-chambered module embodiment, the NOx/SOx abatement occurs in the first of two chambers to receive exhaust gas. The second chamber within the module conditions the exhaust gas after NOx/SOx scrubbing.

Treated exhaust gas is drawn through both chambers from the first opening at near one end of the first chamber to the other end of the first chamber and through an opening at or near the other end of the first chamber wherein the exhaust gas and entrained chemicals are pulled into the first end of the second chamber through an opening, then pulled through the chamber to the other end of the second chamber where the exhaust gas and entrained chemicals leave the second chamber through an opening.

The exhaust gas and entrained chemicals are pulled into and through both chambers by a differential pressure between the first end of the first chamber and the second end of the second chamber. (ClO₂)^(o) gas is drawn into the contemplated and disclosed NOx/SOx reaction chamber through a duct or pipe at a point that is downstream of the first end of the first chamber. In some embodiments the pipe is configured in a pattern that facilitates uniform distribution of the (ClO₂)^(o) gas across the surface of the reaction chamber. (ClO₂)^(o) laden gas is pulled through holes in the pipe that is configured into a pattern within the reaction chamber. Immediately downstream of the point (ClO₂)^(o) is introduced into the reaction chamber, the (ClO₂)^(o) and exhaust gas are mixed by being pulled through a static mixer or mixers of any conventional design. After mixing, the gases continue to be drawn down the length of the reaction chamber while the NOx and SO₂ abatement reactions described in equations [2], [3] and [4] occur.

Example 2

FIG. 1 shows an example of a contemplated process integrated with a NOx SCR scrubber (1-C). The integrated technology package provides a very cost effective way to exceed IMO's 2020 requirements for NOx and SO₂ emissions. The SCR (1-C) cost effectively removes up to 98% of the NOx. The contemplated seawater scrubber (1-I) removes up to 93% of the SOx and a contemplated NOx/SOx scrubber (1-J) completes the NOx and SOx removal to greater than 99.5%. A contemplated NOx/SOx system (1-J) is also capable of treating all of the NOx and SOx in the event the SCR or seawater scrubber are nonoperational. A contemplated ballast water treatment system (1-P) also meets IMO ballast water treatment requirements with (ClO₂)^(o) dosing.

In FIG. 1, the exhaust gas flows through ducting represented by solid black lines. Arrows indicate the direction of gas flow. The combustion source exhaust is treated in the NOx SCR scrubber (1-C) first because this process requires high gas temperatures. With a majority of the NOx removed, the hot exhaust gas is cooled in a heat exchanger (1-F). The heat is transferred from the exhaust gas into water or another gas. This hot water can be used for many applications including reheating the exhaust gas after the final scrubbing stage if there is a desire to reduce the white plume associated with the clean moist exhaust gas.

The majority of the SOx is removed from the cooled exhaust gas in the contemplated seawater pre-scrubber (1-I). It should be understood that this example utilizes seawater, but other types of water can be utilized, as disclosed earlier. This particular seawater SOx scrubber, which includes effectively scrubbing SO₂, can be the technology associated with the contemplated process or the technology from another source. Once the majority of the SOx is removed the cool exhaust gas enters the contemplated NOx/SOx reaction chamber (1-J). This scrubbing stage removes in excess of 99.5% of the remaining SOx and NOx in the gas stream. A contemplated process makes automatic performance adjustments based on data it receives from analytical sensors (1-R) (and others not shown) monitoring the treated exhaust gas stream and other variables. See FIG. 6 for additional details on the control system. This contemplated feature when combined with the pre-treatment modules for NOx (1-C) and pre-treatment module for SOx (1-I) provides 100% backup capability for the integrated system. An exhaust fan (1-Q) provides the motive force necessary to overcome any static pressure generated in the scrubbing sequence or exhaust muffler (1-S).

Ballast water is treated to meet ISO compliance using module (1-P). The ballast water flows in and out of the treatment systems as shown with arrows (1-U) and (1-V). Additional descriptions for FIG. 1 is shown in Table 3.

TABLE 3 KEY EXPLANATION A Fresh air intake to the combustion device (engine, boiler etc.) B Combustion device (engine, boiler etc.) C Selective Catalytic Reduction scrubber (SCR) for NOx D SCR dosing and control unit for urea injection E Urea ((NH₂)₂CO) storage tank F Heat exchanger G Cold water/gas inlet H Hot water/gas outlet I Seawater scrubber (spray if supplied by a contemplated embodiment or packed bed if by another vendor) J Contemplated SOx and NOx scrubber with gas polisher K Seawater conditioning equipment (remove particulate and adjust pH) L Return seawater to ocean M Fresh seawater inlet N Contemplated (ClO₂)° generator and dosing equipment (both gas phase ClO₂ for NOx and SOx and aqueous phase ClO₂ for ballast water dosing) O Chemicals used by (ClO₂)° generator (varies by manufacturer). P Ballast water treatment module using aqueous (ClO₂)° delivered from (N) Q Exhaust blower with optional damper assembly R Gas analyzer for NOx, SOx and (ClO₂)° (data used to regulate contemplated and other scrubbing systems. S Silencer T Clean exhaust retuned to the atmosphere U Treated seawater - See FIG. 3 for detail V Untreated seawater - See FIG. 3 for detail

Example 3

FIG. 2 shows an example of a combination of three contemplated process (SOx pre-scrubber module, NOx/SOx module and ballast water treatment module) in a standalone operating mode. This is configuration does not include an SCR scrubber and therefore has a dramatically lower equipment cost. This standalone configuration is cost effective for large vessels with intermittent use and yachts. FIG. 2 provides more detail on this contemplated exhaust gas treatment process by revealing the internal components of the contemplated NOx/SOx reactor (2-Q) and the proprietary and contemplated seawater pre-treatment scrubber reaction chamber (2-M). The reaction chambers are depicted as cylindrical, but the patent includes other vessel shapes. The reaction chamber is depicted as being vertical, but it functions in any orientation when the alternative tangential side entry (2-AD) shown in FIG. 2 is used. A key for FIG. 2 is found in Table 4.

TABLE 4 KEY EXPLANATION A Vessel inner hull or tankage partition B Ballast water C Vessel outer hull D1 Treated ballast water is pumped back into the sea D2 Treated ballast water is pumped back into holding tank E Ballast water treatment device that utilizes ClO₂ as the disinfectant F Ballast water pumped into the ballast water treatment device G (ClO₂)° suspended in water is pumped from the (ClO₂)° generator to the ballast water treatment device H (ClO₂)° generator. There are many options and this patent can utilize any that deliver the (ClO₂)° without unreacted chemicals or undesirable byproducts. I Chemical storage tanks for the (ClO₂)° generator. Chemical requirement vary by process J (ClO₂)° in gas phase mixed with air or other gas is pulled into the contemplated reaction chamber by differential pressure K Hot exhaust gas from a combustion source or an SCR NOx scrubber L Heat exchanger. The process can transfer heat into gas or liquid for use elsewhere M Contemplated SOx scrubbing vessel N Generic air water separator O Device for pressurizing and regulating the flow of gas or liquid into the nozzles (P). Source for pressurized gas or fluid not shown P Nozzles integrating seawater with high pressure gas and/or liquid to produce liquid droplets with high surface area Q Contemplated reaction vessel for NOx/SO_(x) abatement R Generic static mixer S Mist cloud of (ClO₂)° and NOx/SOx in gas phase - with or without colloidal liquid droplets T Nozzle with or without gas/hydraulic atomization U Exhaust gas with exceptionally low levels of SOx and NOx V Seawater pumped into the contemplated scrubber exhaust gas polishing step W Wastewater pumped to the seawater reclamation device (Z) X Drain for condensate accumulated in the contemplated reaction chamber (Q) Y Seawater pumped into the contemplated SOx scrubber (M) Z Seawater reclamation device that removes particulate and adjusts pH AA Automated chemical metering device for caustic solution such as NaOH AB Tank for caustic solution AC pH probe connected via contemplated sensor and control array (not shown) to chemical metering pump (AA) for addition of caustic material (AA) as required to maintain pH set point AD Duct tangentially entering an end of the contemplated SOx reaction vessel (M) AE Image indicating the swirl introduced into the exhaust gas by (AD)

As shown in FIG. 2, the exhaust gas flows between the double solid black lines. The double lines represent ducting. The diagram begins where exhaust gas is ready to enter the heat exchanger (2-L). For clarity, the heat exchanger's cold/hot liquid or gas flow is omitted. The cooled exhaust gas then travels to the seawater pre-scrubber reaction chamber (2-M) where the majority of the SOx is removed. This diagram depicts the unique features claimed in this patent for a seawater scrubber. The process design also applies to potable water, pure water and brackish water.

The exhaust gas enters seawater SOx pre-treatment scrubber vessel bottom (2-M) or it tangentially enters the vessel side wall (See insert in Figure #2) that shows a detail of the alternate reaction chamber (2-M) gas inlet. In either case the gas is pulled upward by an exhaust gas fan (not shown) on the suction side of the scrubber train. As the gas move toward the center of the reaction chamber (2-M) it mixes with fine mist from gas atomizing and/or hydraulically atomizing nozzles (2-P). The nozzles are oriented in a way that produces multiple layers of fine mist covering the entire diameter of the reaction vessel. The exhaust gas stream is mixed with small diameter and high surface area water droplets. The high surface area of the small droplets improves SOx removal efficiency by enhancing mass transfer between the exhaust gas and liquid seawater, or other waters. This allows the contemplated seawater SOx scrubber to be physically smaller than conventional seawater scrubbers. When exhaust gas enters the reaction vessel tangentially as shown in the detail of FIG. 2, exhaust gas swirls around the circumference of the reaction vessel as it progresses from one end of the vessel to the other. This swirling action increases SOx removal efficiency by increasing gas/liquid mixing. Another attribute of the tangential gas entry is the freedom to orient the reaction vessel in any direction.

A contemplated seawater SOx pre-treatment scrubber is relatively light. There is no water or packing weight so it can be supported with minimal structural support. The small size and light weight and ability to be oriented in any direction reduce retrofit costs and challenges.

Another contemplated seawater SOx pre-treatment scrubber attribute is its automated monitoring of the seawater pH (2-AC) and the addition of an alkaline compound such as NaOH (2-O) to the seawater when the vessel is traveling through an ocean that has lower than normal pH. Contemplated processes and control centers (not shown) monitor and regulate pH and many other variables required to provide safety and optimized SOx removal efficiency.

FIG. 2 shows a contemplated seawater SOx pre-treatment scrubber (2-M) as cylindrical but this is only an example. There is no limitation to or on vessel geometry.

After the majority of the SOx is removed in the seawater pre-treatment scrubber (2-M), the exhaust gas enters one end of the contemplated NOx/SOx scrubber vessel (2-Q). This vessel and the supporting (ClO₂)^(o) generator (1-N)(2-H) are uniquely designed to cost effectively treat just remaining NOx and SOx not treated in the preceding SCR NOx scrubber (1-C) and seawater pre-scrubber (1-I) (2-M) or it can handle the entire load from either of them in the event there is an equipment failure. FIGS. 1 and 2 depicts this NOx/SOx vessel (1-J)(2-Q) in a vertical orientation, but in practice it and the SOx pre-scrubber (1-I)(2-M) can be oriented in any direction. There is no need for the air-water separators (2-N) at the entrance end of the contemplated reaction vessels (2-M) and (2-Q) when the vessel is oriented in any direction other than vertical as shown in FIGS. 1 and 2.

As mentioned earlier, a contemplated NOx/SOx scrubber is relatively light. Once again there is no water or packing or catalyst weight so it can be supported with minimal structural support. The vessel is also smaller in size than an SCR or packed bed scrubber designed to treat a comparable gas flow and contaminant NOx load. Furthermore, a contemplated NOx/SOx scrubber's light weight and ability to be oriented in any direction reduces retrofit costs and challenges.

The exhaust gas is drawn into a contemplated NOx/SOx treatment reaction vessel by an exhaust fan (not shown). The entire vessel and all other vessels and ducts that are a part of the scrubber train are maintained at a net negative pressure when compared to the ambient atmospheric pressure, which provides several advantages. First, it prevents any partially treated exhaust gas from leaking out of the treatment train. Second, it provides process safety by pulling the (ClO₂)^(o) from the generator (2-H) into the contemplated reaction vessel (2-M). Third, this provides process safety by eliminating backpressure on the combustion device. Contemplated instrumentation and process control array (not shown) maintains the scrubber train negative pressure (and other variables) despite pressure fluctuations caused by damper position changes in complicated scrubbing systems designed to treat exhaust gas from multiple combustion sources. A contemplated sensor and control array (not shown) includes differential pressure sensor(s) that provide data used to regulate the exhaust fan speed as required to maintain a negative pressure set point or trigger an alarm if the negative pressure cannot be maintained. A contemplated control system is shown in FIG. 5 and Table 7.

The (ClO₂)^(o) gas is drawn into the contemplated and disclosed NOx/SOx reaction chamber (2-Q) down stream of and near the point that the exhaust gas is introduced into the chamber (2-Q). Then immediately downstream of the point (ClO₂)^(o) and exhaust gas are introduced the gases are pulled through a static mixer of any conventional design. After mixing, the gases continue down the length of the reaction chamber (2-Q) while the NOx and SO₂ abatement reactions described in equations [2], [3] and [4] occur. 5NO+2(ClO₂)^(o)+H₂O→5NO₂+2HCl  [2] 5NO₂+(ClO₂)^(o)+3H₂O→5HNO₃+HCl  [3] 5SO₂+2(ClO₂)^(o)+6H₂O→5H₂SO₄+2HCl  [4] 6SO₃ ⁻²+2(ClO₂)^(o)12H⁺→H₂S₂O₆+4H₂SO₄+2HCl  [5]

Laboratory and in-the-field studies have shown that the equations noted above have different rates of reaction and all three have equilibrium constants that strongly favor the right side of the equation. Equation [4] and [5] are faster than equation [2], and equation [2] is faster than equation [3]. These observations and other related studies lead to the recognition of the enormous application flexibility available in this contemplated technology package including but not limited to the production of commercially viable products from reaction effluents and strategic integration with other SOx and NOx abatement processes.

FIG. 1 shows the synergistic value of combining three or more technologies in a way that delivers economic and performance benefits that are greater than the sum of the benefits available from the individual technologies. The pre-treatment SCR technology removes the bulk of the NOx more cost effectively than the contemplated NOx/SOx process but the SCR is unable to reach the removal efficiencies available through the use of contemplated NOx/SOx processes and apparatus. Similarly, the pre-treatment seawater SOx scrubber removes these compounds at a lower operating cost but is unable to reach the high removal efficiency provided by the contemplated NOx/SOx process. And as previously noted, the combined technologies provide the most cost effective 100% backup protection for the vessel or land-based industry. The combined technology also requires with far less space than other imaginable 100% redundant options.

A contemplated NOx/SOx reaction chamber (2-Q) is smaller than any other technology for use for the disclosed purposes known at this time including SCR and wet scrubbing, because:

-   -   Contemplated NOx/SOx reactions have the propensity to be gas         phase reaction that only requires the (ClO₂)^(o) to meet/contact         the NOx molecule. It does not require a catalyst that is         necessary in the SCR technology. The SCR technology requires a         larger area and volume than contemplated NOx/SOx processes,         because the SCR reaction requires three molecules to meet at the         same time and that is statistically and literally more         difficult, because it requires more opportunities for a         “meeting” than is necessary in the contemplated NOx/SOx process.         In the SCR process, a NOx molecule must simultaneously meet a         urea or ammonia molecule at the same time it meets with the         catalyst. This random act becomes more difficult as the         concentration of NOx diminishes. This is overcome in the SCR         process by providing several layers of catalyst. When high         removal efficiencies are required there can be four or more         layers each requiring space within the SCR reaction chamber.     -   Contemplated NOx/SOx processes do not need the volume necessary         to provide sufficient reaction time for slow liquid phase         reactions to occur. Liquid phase/gas phase reaction of the type         done in all wet scrubbing systems require more volume than the         contemplated NOx/SOx scrubber because wet scrubbers require time         for the NOx molecules in the exhaust gas to penetrate the         gas/liquid barrier. This is particularly important when treating         NO (NOx from combustion is about 95% NO), because of NO's low         solubility in water: 0.0098 g/100 ml at 0° C.     -   Contemplated NOx/SOx processes are not poisoned or contaminated         by sulfur products found in marine fuel. A contemplated NOx/SOx         process does not have any catalyst to become contaminated or         packing to become clogged. This unwanted catalyst poisoning is         described in greater detail later.

A contemplated NOx/SOx process is not limited to the fast gas phase chemistry described above. Although slower, the (ClO₂)^(o), as suspended in a liquid, can be introduced into the contemplated and disclosed reaction chamber (2-Q). When this done, the process requires a larger reaction chamber to accommodate the reaction time necessary to evaporate the droplets and/or undergo the gas/liquid mass transfer as described above. The gas phase reactions only necessitate a reaction vessel (2-Q) of sufficient volume to provide 0.5 second residence time. The reaction residence time is increased to as much as 1.5 seconds when (ClO₂)^(o) is introduced into the reaction vessel (2-Q) as a liquid.

Once the exhaust gas and the (ClO₂)^(o) have had sufficient time to react and reach a desired process equilibrium, the mixture is ready for a subsequent reaction to produce a commercially viable product from reaction byproducts or the reaction byproducts can be neutralized and discarded as waste that may require further treatment before it is disposed in a responsible way. In this marine application, the second portion of the NOx/SOx treatment/reaction chamber (2-Q) is used to transfer the reaction products into seawater. The seawater or other water used as a medium to capture the NOx/SOx reaction products may have additional metal hydroxide components or other alkaline components. If required, the wash liquid will receive subsequent neutralization or treatment before being returned to the sea. If space is available, the vessels could be fitted with a recycling program that produced a commercially viable compounds s from the NOx/SOx reaction products.

Returning to differences in the rates of reaction for equations [2], [3] and [4], when SO₂ is present in a NOx/SO_(x) exhaust gas mix, the SO₂ will always react first. Therefore, economic viability necessitates pre-treatment of SO₂ in the gas stream, when present in large quantities, with a pretreatment process that utilizes chemicals with lower cost than the chemicals used in the contemplated NOx/SOx process and save the contemplated NOx/SOx process for removal of the remaining NOx/SOx that the precursor processes are unable to remove.

The fact that equation [2] is dramatically faster than equation [3] provides an opportunity for great flexibility in the application of contemplated processes, because it allows the (ClO₂)^(o) mixed with the exhaust gas to selectively react with the NO portion of the NOx present until a desired ratio of NO/NO₂ is obtained. This is particularly applicable when contemplated methods and processes are treating NOx generated in a combustion process because that NOx typically contains 90-95% NO.

Additional research has demonstrated a 50/50 mixture of NO/NO₂ will react efficiently with NaOH when promoted by a sub-stoichiometric ratio of any of several compounds. The reaction of the 50/50 NOx mix is not less than 30% more efficient than a reaction between NaOH and a mixture with more NO than NO₂ that is not promoted with the sub-stoichiometric ratios of promoters described in Table 1.

Bench and pilot studies at ambient temperatures and slightly negative pressure (3″ H₂O column) provide the following results: 2NaOH+NO₂+NO+(**)→2NaNO₂+H₂O  [9]

The reaction promoters described in Table 1 were found to be effective at concentration between 5-10% (molar basis) of the total NaOH used in the reaction. There was no identified improvement in reaction rate or shift in the reaction equilibrium when higher concentrations of the promoters were added.

TABLE 1 ** REACTION PERCENT REMOVAL PROMOTING COMPOUNDS EFFICIENCY H₂O₂ 85-90% O3 95% NaClO 90-95% Ca(ClO)₂ 95-100%

This two-step process reduces the overall operational cost of NOx abatement, because it only requires a minimal amount of (ClO₂)^(o) necessary to create a 50/50 NO/NO₂ balance in the NOx ratio and primarily utilizes less expensive NaOH and reaction promoter to remove the NOx from the gas stream.

The secondary process depicted in FIG. 2, as an extended reaction chamber, utilizes seawater, or other types of water, as a solvent for contemplated NOx/SOx reaction byproducts. This is an optimum solution for a seagoing vessel and land based facilities near the sea, but this is not the only option. As previously noted, the reaction products could be converted into commercially viable compounds if space and budget allowed. In this example, the HCl, HNO₃ and H₂SO₄ acids formed in equation [2], [3] and [4] are removed from the exhaust gas stream and partially neutralized by the seawater's alkalinity in an attached secondary mist treatment. Any additional neutralization occurs in the process water reclamation step (2-Z). The second portion of the contemplated reaction chamber (2-Q) contains an air water separator (2-N) when the chamber is mounted vertically. This is not required in horizontal or near horizontal applications. In other applications, this secondary reaction chamber could be used to generate commercially viable products.

FIG. 2 also shows the contemplated (ClO₂)^(o) generator (3-H) providing (ClO₂)^(o) that has been suspended in water to the ballast water treatment device (3-E). Related literature discloses that ClO₂ dosed at 5 ppm concentration into ballast water eradicates most planktonic organisms and bacteria.

Example 4

FIG. 3 shows in detail the actual (ClO₂)^(o) dosing and control methodology included in the rectangle marked “E” on FIG. 2. The technology described in this ballast water treatment is intrinsically safe because the process does not proceed unless the seawater pump (3-S) is operating. The (ClO₂)^(o) is only drawn out of a (ClO₂)^(o) storage tank (3-P) by vacuum generated in a venturi (3-N) and that only occurs when pump (3-S) is operating. This prevents over dosing or chemical spills due to siphoning errors or pumping errors that could occur if the (ClO₂)^(o) was pumped out of the storage tank (3-P). Table 5 shows a series of information related to FIG. 3 for reference.

TABLE 5 KEY EXPLANATION A Vessel inner hull or tankage partition B Ballast water C Outer hull of the vessel D1 Treated ballast water is pumped back into the sea D2 Treated ballast water is pumped back into holding tank E Ballast water treatment device that utilizes ClO₂ as the disinfectant. F Ballast water pumped into the ballast water treatment device G (ClO₂)° suspended in water is pumped from the (ClO₂)° generator to the ballast water treatment device H (ClO₂)° generator. There are many options and this patent can utilize any that deliver the (ClO₂)° without unreacted chemicals or undesirable byproducts. I Chemical storage tanks for the (ClO₂)° generator. Chemical requirement vary by process J Basic compound such as sodium hydroxide K Automated chemical metering pump L pH probe M Static mixer N Venturi O Automated valve and flow indicator P Storage tank for water with suspended (ClO₂)° Q Vent to open air R Supply of (ClO₂)° suspended in water from (ClO₂)° generator (H) S Automated variable speed pump T Analytical instrument for measurement of (ClO₂)° suspended in water U Instrument for transmitting water flow rate with local display

Example 5

FIG. 4 shows a contemplated reaction chamber and system for a single stage pretreatment and treatment system. This reaction chamber includes three separate chemical treatments to the exhaust gas. The first removes the majority of the SOx in a pre-treatment (4-M-1). The second treatment removes essentially all of the NOx/SOx (40M-2) and the final treatment (4-M-3) removes the NOx/SOx reaction products from the exhaust gas stream as salts or commercially viable products. Table 6 shows a series of information related to FIG. 4 for reference.

TABLE 6 KEY EXPLANATION A Vessel inner hull or tankage partition B Ballast water C Vessel outer hull D1 Treated ballast water is pumped back into the sea D2 Treated ballast water is pumped back into holding tank E Ballast water treatment device that utilizes ClO₂ as the disinfectant F Ballast water pumped into the ballast water treatment device G (ClO₂)° suspended in water is pumped from the (ClO₂)° generator to the ballast water treatment device H (ClO₂)° generator. There are many options and this patent can utilize any that deliver the (ClO₂)° without unreacted chemicals or undesirable byproducts. I Chemical storage tanks for the (ClO₂)° generator. Chemical requirement vary by process J (ClO₂)° in gas phase mixed with air or other gas is pulled into the NOx/SOx reaction chamber by differential pressure. Alternatively this can be liquid with suspended (ClO₂)°. K Hot exhaust gas from a combustion source or an SCR NOx scrubber L Heat exchanger. The process can transfer heat into gas or liquid for use elsewhere M-1 SOx pretreatment end of single scrubbing vessel M-2 NOx/SOx end of a single scrubbing vessel M-3 Gas polishing post treatment module N Generic air water separator O Device for pressurizing and regulating the flow of gas or liquid into the nozzles (P). Source for pressurized gas or fluid not shown P Nozzles integrating seawater or metal oxide solution with high pressure gas and/or liquid to produce liquid droplets with high surface area Q (ClO₂)° gas diffusion device or liquid spray nozzle for NOx/SO_(x) abatement in M-2 portion of the reaction chamber R Generic static mixer S Mist cloud of (ClO₂)° and NOx/SOx in gas phase - with or without colloidal liquid droplets in the M-2 portion of the reaction chamber T Nozzle with or without gas/hydraulic atomization U Exhaust gas with exceptionally low levels of SOx and NOx V Seawater pumped into the M-3 gas polishing module W Wastewater pumped to the seawater reclamation device (AA) X-1 Automated chemical metering device for metal oxide solution such as NaOH X-2 Automated chemical metering device for metal oxide solution such as NaOH Y Seawater pumped into the SOx pretreatment portion of scrubber (M-1) Z-1 pH probe connected via control panel (not shown) to chemical metering pump (X-1) for addition of metal oxide material (Y) as required to maintain pH set point Z-2 pH probe connected via control panel (not shown) to chemical metering pump (X-2) for addition of metal oxide (Y) as required to maintain pH set point AA Seawater reclamation device that removes particulate and adjusts pH AB Seawater inlet AC Seawater discharge AD Duct tangentially entering an end of the TIP SOx reaction vessel (M) AE Image indicating the swirl introduced into the exhaust gas by (AD)

Example 6

FIG. 5 shows a contemplated three stage treatment occurring in a “two-connected reaction chamber and system” configuration. The first stage SOx pre-treatment occurs in the first reaction chamber module (5-M). The second stage NOx/SOx treatment and third stage gas cleaning occur in the second module (5-Q). The ballast water treatment module (5-E) is also shown. Table 7 shows a series of information related to FIG. 5 for reference.

TABLE 7 KEY EXPLANATION A Vessel inner hull or tankage partition B Ballast water C Vessel outer hull D1 Treated ballast water is pumped back into the sea D2 Treated ballast water is pumped back into holding tank E Ballast water treatment device that utilizes ClO₂ as the disinfectant F Ballast water pumped into the ballast water treatment device G (ClO₂)° suspended in water is pumped from the (ClO₂)° generator to the ballast water treatment device H (ClO₂)° generator. There are many options and this patent can utilize any that deliver the (ClO₂)° without unreacted chemicals or undesirable byproducts. I Chemical storage tanks for the (ClO₂)° generator. Chemical requirement vary by process J (ClO₂)° in gas phase mixed with air or other gas is pulled into the TIP reaction chamber by differential pressure K Hot exhaust gas from a combustion source or an SCR NOx scrubber L Heat exchanger. The process can transfer heat into gas or liquid for use elsewhere M TIP SOx scrubbing vessel N Generic air water separator O Device for pressurizing and regulating the flow of gas or liquid into the nozzles (P). Source for pressurized gas or fluid not shown P Nozzles integrating seawater with high pressure gas and/or liquid to produce liquid droplets with high surface area Q TIP reaction vessel for NOx/SO_(x) abatement R Generic static mixer S Mist cloud of (ClO₂)° and NOx/SOx in gas phase - with or without colloidal liquid droplets T Nozzle with or without gas/hydraulic atomization U Exhaust gas with exceptionally low levels of SOx and NOx V Seawater pumped into the TIP scrubber exhaust gas polishing step W Wastewater pumped to the seawater reclamation device (Z) X Drain for condensate accumulated in the TIP reaction chamber (Q) Y Seawater pumped into the TIP SOx scrubber (M) Z Seawater reclamation device that removes particulate and adjusts pH AA Automated chemical metering device for caustic solution such as NaOH AB Tank for caustic solution AC pH probe connected via TIP sensor and control array (not shown) to chemical metering pump (AA) for addition of caustic material (AA) as required to maintain pH set point AD Duct tangentially entering an end of the TIP SOx reaction vessel (M) AE Image indicating the swirl introduced into the exhaust gas by (AD)

Example 7

FIG. 6 shows a contemplated sensor and automated control configuration for the integrated exhaust and ballast water treatment modules. Table 8 shows a series of information related to FIG. 6 for reference.

TABLE 8 KEY EXPLANATION A Central control panel. Many of the modules have local control panels, but all can subordinate to remote control by the central control panel B Combustion exhaust source - typically engine or boiler C Pretreatment NOx destruction by Selective Catalytic Reduction (SCR) - or equal D Automated chemical dosing for SCR E Chemical storage tank for SCR F Heat exchanger(gas/gas or gas/liquid) G Treated water discharge into sea H Water treatment module I SO₂ Pretreatment module J NOx/SOx treatment module K Exhaust blower L Exhaust stack M (ClO₂)° generator module N Chemical storage for (ClO₂)° generator module O Ballast water treatment module 1 Sensor- Control panel unauthorized access 2 Sensor- Exhaust gas temperature and flow 3 Analog/digital performance confirmation data from local control system 4 Sensor-Tank level 5 Analog/digital performance confirmation data from local control system 6 Sensor- Gas temperature, coolant liquid/gas temperature Control - Coolant water/gas flow rate 7 Sensors - pH, Total Dissolved Solids, flow and others as required by regulations Control - Bypass to holding tank if water quality set points are not met/shut down system 8 Analog/digital performance confirmation data from local control system Control - Chemical dosing rate as required to meet water quality performance set points 9 Sensor - SO₂ level at vessel discharge, nozzle gas flow and pressure, Nozzle liquid flow and pressure, pH of liquid feed to nozzle, liquid level in reaction vessel Control - Liquid and gas flow to nozzles, rate of metal hydroxide addition to liquid feed to nozzles, pump to remove liquid from reaction vessel 10 Sensor - Chamber differential pressure across static mixer and compared to ambient atmospheric pressure, liquid level in vessel Control - Exhaust fan speed as required to maintain differential pressure set point between vessel and atmosphere 11 Sensor - Nozzle liquid pressure and flow, liquid level in compartment Control - Liquid flow rate to nozzle 12 Control - fan speed (VFD) 13 Sensor - SO₂, NOx, (ClO₂)° gas flow rate Control - (ClO₂)° flow rate 14 Sensor - (ClO₂)° flow rate 15 Sensor - many sensors - varies by (ClO₂)° generator type Control - all functions of (ClO₂)° generator 16 Sensor - (ClO₂)° flow rate 17 Sensor - Tank level 18 Sensors - (ClO₂)° level in pre and post treated seawater, seawater flow rate, pH of water, liquid level in tanks Controls - Chemical metering of metal hydroxide addition, flow rate of (ClO₂)°, selection of valves as required to operate the system

Example 8

Two systems that have all three components: pretreatment, treatment, and post-treatment are shown as a part of this Example—in FIGS. 7 and 8.

FIG. 7 shows the exhaust gas treatment portion of the contemplated process in an expanded view. The exhaust SOx pretreatment is in one module and a second module combines NOx/SOx scrubbing and post scrubbing gas treatment. Table 8 shows the key components of FIG. 7.

TABLE 9 KEY EXPLANATION A Exhaust gas from combustion source. B Condensate drain from H-1 & H-2 chamber C Air water separator. Only necessary when reaction vessel is in the vertical orientation. D Pressurized gas for gas atomized nozzle E Nozzle - can be gas atomized or liquid atomized or in some instances fine hydraulic nozzle F Pressurized stream of seawater and/or other waters that have alkaline material added to increase pH G Fine mist cloud mixture of high pH liquid water and exhaust gas H-1 SOx scrubbing stage H-2 NOx/SOx scrubbing stage H-3 Gas conditioning stage - removes/converts reaction products from NOx/SOx scrubbing into salts or other compounds. I (ClO2)° addition as gas or fine mist J Static mixer(s) K Gas mixture of (ClO2)° and exhaust gas L Condensate drain from gas conditioning chamber M Pressurized stream of compounds selected as required to accomplish a specific gas conditioning result. N Nozzle can be hydraulic atomized or hydraulic nozzle. O Fine mist cloud mixture of exhaust gas and process specific compounds P Demister Q Cleaned exhaust gas R Describes swirl motion introduced into the exhaust gas when exhaust gas is introduced into the reaction chamber through a duct that is tangentially oriented to the chamber wall

FIG. 8 shows the exhaust gas treatment portion of the contemplated process in an expanded view. The exhaust SOx pretreatment, NOx/SOx scrubbing and post scrubbing gas treatment are combined in a single module. Table 8 also applies to the key components of FIG. 8.

Thus, specific embodiments, methods of using chlorine dioxide to remove NOx and SOx from marine exhaust, including pre-treatment and post-treatment solutions, have been disclosed. It should be apparent, however, to those skilled in the art that many more modifications besides those already described are possible without departing from the inventive concepts herein. The inventive subject matter, therefore, is not to be restricted except in the spirit of the disclosure herein. Moreover, in interpreting the specification and claims, all terms should be interpreted in the broadest possible manner consistent with the context. In particular, the terms “comprises” and “comprising” should be interpreted as referring to elements, components, or steps in a non-exclusive manner, indicating that the referenced elements, components, or steps may be present, or utilized, or combined with other elements, components, or steps that are not expressly referenced. 

I claim:
 1. A pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a water supply line that supplies a liquid; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets, wherein each droplet comprises a diameter, that create a high surface area of liquid across the interior surface of the reaction chamber; a pH sensor coupled to the water supply line; at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas or the flue gas by converting at least some of the SOx molecules to sulfate ions.
 2. The pretreatment system of claim 1, wherein the liquid that the water supply line supplies comprises seawater, pure water with additional metal hydroxide, carbonates, bicarbonates, ammonia components, or a combination thereof potable water with additional metal hydroxide, carbonates, bicarbonates, ammonia components, or a combination thereof, tainted water with additional metal hydroxide, carbonates, bicarbonates, ammonia components, or a combination thereof.
 3. The pretreatment system of claim 1, wherein the mean diameter of the small liquid droplets is less than about 30 microns.
 4. The pretreatment system of claim 1, wherein the mean diameter of the small liquid droplets is less than about 20 microns.
 5. A pretreatment method or process for removing SOx molecules from marine vessel exhaust or flue gas, includes: providing a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; providing a water supply line that supplies a liquid; providing an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; providing a gas atomization nozzle array that is coupled to the water supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets, wherein each droplet comprises a diameter, that create a high surface area of liquid across the interior surface of the reaction chamber; providing a pH sensor coupled to the water supply line; providing at least one chemical metering pump coupled to the pH sensor and the water supply line, wherein the pump can provide an alkaline material into the water supply line to adjust the pH of the water before it is sprayed into the reaction chamber; and providing a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecule from the exhaust gas by converting it to sulfate ions.
 6. A pretreatment system or apparatus for removing SOx molecules from marine vessel exhaust or flue gas, is disclosed that includes: a reaction chamber, comprising an interior area, a gas inlet at or near a first end of the chamber, and a gas outlet at or near a second end of the chamber; a seawater supply line that supplies seawater; an exhaust or flue gas supply line that supplies an exhaust gas or a flue gas, wherein the line is coupled with the inlet of the reaction chamber; a gas atomization nozzle array that is coupled to the seawater supply line and the reaction chamber, wherein the nozzle array sprays a blanket layer of small liquid droplets, wherein each droplet comprises a diameter, that create a high surface area of seawater across the interior surface of the reaction chamber; a pH sensor coupled to the seawater supply line; at least one chemical metering pump coupled to the pH sensor and the seawater supply line, wherein the pump can provide an alkaline material into the seawater supply line to adjust the pH of the seawater before it is sprayed into the reaction chamber; and a drain coupled to the reaction chamber that removes liquid that accumulates in the reaction chamber, wherein the system or apparatus removes at least some of the SOx molecules from the exhaust gas or the flue gas by converting it to sulfate ions.
 7. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 1, wherein the second end of the pretreatment reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; and an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the first reaction chamber travels from the outlet end of the first reaction chamber to the first end or inlet end of the second reaction chamber.
 8. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 1, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; and an inlet for introducing chlorine dioxide into the reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with non-ionic chlorine dioxide.
 9. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 6, wherein the second end of the pretreatment reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; and an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the first reaction chamber travels from the outlet end of the first reaction chamber to the first end or inlet end of the second reaction chamber.
 10. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 6, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; and an inlet for introducing chlorine dioxide into the reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with non-ionic chlorine dioxide.
 11. A method of NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: providing the pretreatment system of claim 1, wherein the second end of the reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; and providing an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the first reaction chamber travels from the outlet end of the first reaction chamber to the first end or inlet end of the second reaction chamber; and treating the exhaust gas or gas to be treated with chlorine dioxide.
 12. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 1, wherein the second end of the pretreatment reaction chamber is coupled with a first end or an inlet end of a second reaction chamber; an inlet for introducing chlorine dioxide into the second reaction chamber, wherein the second reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas or gas to be treated from the pretreatment reaction chamber travels from the outlet end of the pretreatment reaction chamber to the first end or inlet end of the second reaction chamber; and an inlet for a post-treatment chamber that is coupled with the second end of the second reaction chamber, wherein at least one product of the second reaction chamber travels into the inlet of the post-treatment chamber.
 13. The NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas of claim 12, wherein the at least one product of the second reaction chamber comprises at least one mineral acid.
 14. The NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas of claim 13, wherein seawater, potable water, pure water, or tainted water with additional metal hydroxides, carbonates, bicarbonates, or ammonia compounds are added or introduced to neutralize the at least one mineral acid or convert the at least one mineral acid into another component.
 15. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 1, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; an inlet for introducing chlorine dioxide into the pretreatment reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with non-ionic chlorine dioxide; and an inlet for the introduction of seawater, potable water with additional metal hydroxides, tainted water with additional metal hydroxides, or pure water with additional metal hydroxides in order to neutralize the mineral acids that are produced reaction chamber.
 16. A NOx, SOx, or a combination thereof abatement or scrubbing system for marine vessel flue gas, comprising: the pretreatment system of claim 6, wherein the pretreatment reaction chamber is also utilized for scrubbing NOx, SOx, or a combination thereof; an inlet for introducing chlorine dioxide into the pretreatment reaction chamber, wherein the reaction chamber is equipped with one or more turbulence inducing devices configured for inducing turbulence, wherein the turbulence inducing device is a stationary device, and wherein the exhaust gas remains in the reaction chamber for treatment with chlorine dioxide; and an inlet for the introduction of seawater, potable water with additional metal hydroxides, tainted water with additional metal hydroxides, or pure water with additional metal hydroxides in order to neutralize the mineral acids that are produced in the reaction chamber.
 17. The system of claim 12, wherein a post-treatment process is activated in the post-treatment chamber.
 18. The system of claim 17, wherein the post-treatment process comprises an acid neutralization post-treatment process, a sodium nitrate/nitrate production post-treatment process, an ammonium sulfate production post-treatment process, or an ammonium nitrate and ammonium chloride production post-treatment process. 